WO2010042948A2 - Composés tétratopiques du phényle, matière structurante organométallique correspondante, et élaboration après assemblage - Google Patents

Composés tétratopiques du phényle, matière structurante organométallique correspondante, et élaboration après assemblage Download PDF

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WO2010042948A2
WO2010042948A2 PCT/US2009/060524 US2009060524W WO2010042948A2 WO 2010042948 A2 WO2010042948 A2 WO 2010042948A2 US 2009060524 W US2009060524 W US 2009060524W WO 2010042948 A2 WO2010042948 A2 WO 2010042948A2
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metal
organic framework
tetratopic
building block
carboxylic acid
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PCT/US2009/060524
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WO2010042948A3 (fr
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Omar K. Farha
Joseph T. Hupp
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Northwestern University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
    • C07F3/06—Zinc compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
    • B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/41—Preparation of salts of carboxylic acids
    • C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C63/00—Compounds having carboxyl groups bound to a carbon atoms of six-membered aromatic rings
    • C07C63/33—Polycyclic acids
    • C07C63/331—Polycyclic acids with all carboxyl groups bound to non-condensed rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
    • C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic Table without C-Metal linkages
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/20—Organic adsorbents
    • B01D2253/204—Metal organic frameworks (MOF's)

Definitions

  • the present invention relates to tetracarboxylic acid and related species. These compounds can be used in a crystalline metal-organic framework. More specifically, the invention relates to a tetratopic phenyl and related metal-organic framework compounds. Such metal-organic framework compounds of the present invention are suitably used in catalysis, gas storage, sensing, biological imaging, drug delivery and gas adsorption separation.
  • Crystalline metal-organic frameworks comprise a rapidly growing class of permanently microporous materials. 1 They are characterized by low densities, high internal surface areas, and uniformly sized pores and channels. These properties point to a broad range of potential applications, including chemical separations, 2 catalysis, 3 gas storage and release, 4 biological imaging, 5 and drug delivery. 6 Many of these applications require comparatively large cavities.
  • MOF syntheses typically produce catenated structures, thereby reducing cavity size, increasing density, diminishing vapor-uptake capacity and diminishing gravimetric surface area (See Figure 1). In most cases non-catenated MOFs are desired, but experimentally catenated structures are often obtained.
  • MOFs having: a) cavities and pores of optimal size, shape, and/or chirality, and b) interior and/or exterior surfaces of suitable chemical composition.
  • Systematic (i.e. predictable) tunability of pore size and, to some extent, surface chemical composition has indeed been nicely demonstrated for certain families of MOFs. 7
  • even minor changes in synthesis conditions or strut composition can lead - seemingly unpredictably - to significant differences in cavity-defining metal- node/organic-strut coordination and/or degree of framework catenation.
  • certain desirable functional groups may be difficult to incorporate directly into MOFs, either due to thermal instability under materials synthesis conditions 9 or because of competitive reaction with intended framework components. Together, these complications can make direct assembly of MOFs that are optimal for specific applications particularly challenging.
  • the present invention can be directed to a class of metal-organic framework building blocks comprising tetratopic carboxylic acids and related compounds.
  • a building block can feature a phenyl ring core, substituted at the 1- , 2-, 4-, and 5-positions with substituted phenyl ring spacers.
  • the carboxylic acids, used to bind metal ion or cluster nodes, can be located at the 4-postion of each phenyl ring spacer, although other positioning can be employed.
  • this invention can be directed to a broad range of tetracarboxylic acid and related species; e.g., 4 l ,5'-bis(4-carboxyphenyl)-[l,r:2',r ⁇ - terphenyl]-4,4"-dicarboxylic acid (named according to ChemDraw Ultra 12.0; other names include 4,4',4",4'"-benzene-l,2,4,5-tetrayl-tetrabenzoic acid or 1,2,4,5- tetrakis(4-carboxyphenyl)benzene, 2.
  • 4 l ,5'-bis(4-carboxyphenyl)-[l,r:2',r ⁇ - terphenyl]-4,4"-dicarboxylic acid named according to ChemDraw Ultra 12.0; other names include 4,4',4",4'"-benzene-l,2,4,5-tetrayl-tetrabenzoic acid or 1,2,4,5
  • deprotonated 2 would, as: a) an unusually shaped molecule, resist formation of catenated MOFs, b) a tetra- topic building block, produce robust frameworks, and c) a nonplanar moiety, potentially produce a 3D framework. Such characteristics can favor the formation of comparatively large cavities which can be shown experimentally. Additionally, representative of various other embodiments of this invention, 2 can readily form more complex, non-catenated MOF materials when combined with other candidate organic struts. In accordance with this invention, various other compounds can be prepared using synthetic techniques of the sort described herein, or straightforward modifications thereof, as would be understood by those skilled in the art made aware of this invention, (see, e.g., Figures 3, 4, and 5).
  • a robust, non-catenated, and permanently microporous metal-organic framework (MOF) material has been synthesized by combining a new nonplanar ligand, 4,4',4",4'"-benzene- 1,2,4, 5-tetrayl- tetrabenzoic acid, with a Zn(II) source under solvo thermal conditions.
  • the new material features cavities that are readily modified via activation and functionalization of framework nodes (as opposed to struts).
  • Preliminary investigation of the "empty cavity” version of the material and six cavity-modified versions reveals that modification can substantially modulate the MOF's internal surface area, pore volume, and ability to sorb molecular hydrogen.
  • a metal site component can, without limitation, comprise another metal ion capable of coordination chemistry comparable to or available through Zn(II).
  • the invention can also be directed to a gas adsorption separation process characterized by adsorption separation of components in a gas by contacting the gas with a MOF of the invention.
  • a gas adsorption separation process characterized by adsorption separation of components in a gas by contacting the gas with a MOF of the invention.
  • Such a process can be employed to reduce the emission of gases from industrial processes.
  • the MOFs of the instant invention can be used for the adsorption of such gases as, for example, H 2, CO 2 , N 2 and CH 4 .
  • the MOF of the invention acts as an adsorbent with high selectivity for one or more gases.
  • Fig 1 is a diagram of a A) noncatenated structure and a B) catenated structure.
  • Figs 2A-C represent ligands of the sort useful in accordance with this invention.
  • Fig 3 is an example of a noncatenated MOF with a large cavity that can be used for hydrogen, carbon dioxide and methane storage and/or separation.
  • Fig 4 is another example of a noncatenated MOF with a large cavity that can be used for hydrogen, carbon dioxide and methane storage and/or separation.
  • Fig 5 is an example of a noncatenated MOF with a large cavity that can be used for catalysis.
  • Fig 6 depicts crystallographically derived MOF 3: (A) structure of 3, (B) topology and connectivity of 3, (C) ac-plane, looking down b-channels, and (D) ab-plane, looking down c-channels (coordinated DMF molecules are shown in space-filling fashion, while non-coordinated solvent molecules (disordered) are omitted from the structure representations).
  • Fig 7 depicts (A) thermogravimetric analyses of 3 as synthesized (black), 4 (red), and 4 resolvated (blue); and (B) first-derivative thermogravimetric analyses plots for solvent-evacuated, py-R-modified MOFs. For presentation clarity, curve for MOF modified with 8 is omitted.
  • Fig 8 shows the 1 H NMR of dissolved 3' (top), 4 (middle), and 4+5 (bottom).
  • Fig 9 depicts the isotherms for uptake of H 2 at 77K and 1 atm. by: 4+9 (bottom), 3' (middle), and 4 (top).
  • Fig 10 depicts H 2 uptake versus pore volume (red, open squares) and surface area (blue, diamonds).
  • Fig 11 depicts the simulated (bottom) and "as synthesized" bulk (top) powder x-ray diffraction patterns for 3.
  • Fig 12 shows the 1 NMR spectra in D 2 SO 4 /D 2 O of 3' (bottom) and 4 (top).
  • Fig 13 shows the 1 NMR spectra in D 2 SO 4 /D 2 O of 3' (top), 4 (middle) and 4+5 (bottom).
  • Fig 14 shows the 1 NMR spectra in D 2 SO 4 /D 2 O of 4+5.
  • Fig 15 shows the 1 NMR spectra in D 2 SO 4 /D 2 O of 4+6.
  • Fig 16 shows the 1 NMR spectra in D 2 SO 4 /D 2 O of 4+7.
  • Fig 17 shows the 1 NMR spectra in D 2 SO 4 /D 2 O of 4+8.
  • Fig 18 shows the 1 NMR spectra in D 2 SO 4 /D 2 O of 4+9.
  • Fig 19 depicts thermogravimetric analyses plots for the MOFs of the invention.
  • Fig 20 depicts first-derivative thermogravimetric analyses plots for the MOFs of the invention.
  • Fig 21 depicts first-derivative thermogravimetric analyses plots for 4+6 evacuated at 150 0 C (top) then resolvated with CHCl 3 (bottom).
  • Fig 22 depicts CO 2 isotherms at 273K. Desorption curves are omitted for clarity.
  • Fig 23 depicts H 2 isotherms at 77K. Desorption curves are omitted for clarity.
  • Fig 24 depicts H 2 isotherms at 77K and 87K (black squares) and virial equation fits (red line) for 3' (I).
  • Fig 25 depicts H 2 isotherms at 77K and 87K (black squares) and virial equation fits (red line) for 4 (II).
  • Fig 26 depicts heats of adsorption ( ⁇ H ads ) for H 2 in 3'(blue) and 4 (black).
  • Fig 27 depicts adsorption isotherms of CO 2 , N 2 , and CH 4 in 3', 4, and 4+9 at 298 0 K: (a) full pressure range, (b) low pressure range (CH 4 isotherms are omitted for clarity).
  • Fig 28 shows ideal adsorption solution theory selectivities of (a) CO 2 over N 2 , and (b) CO 2 over CH 4 for equimolar binary mixtures in 3', 4, and 4+9 at 298°K.
  • Fig 29 shows ideal adsorption solution theory selectivities of CO 2 over N 2 in 9 at different pressures and mixture compositions.
  • Fig 30 depicts adsorption rates of CO 2 and N 2 in 4+9 at 298°K (at the 1 st adsorption points), mt is the amount adsorbed at time t, and me is the equilibrium amount adsorbed.
  • the invention relates to a new tetracarboxylic acid species (4,4',4",4 m - benzene-1, 2,4,5 -tetrayl-tetrabenzoic acid, 2), and salts thereof, as shown in Scheme 1.
  • a deprotonated 2 was found to be a) an unusually shaped molecule, resisting formation of catenated MOFs, b) a tetra- topic building block, producing robust frameworks, and c) a nonplanar moiety, producing a 3D framework.
  • TGA Thermogravimetric analysis of 3 revealed mass losses at about 100 0 C and 175°C, assigned to free and coordinated DMF, respectively; no further mass loss occurs until 425°C ( Figure 7A).
  • Heating 3 under vacuum at 100 0 C allows for selective removal of non-coordinated DMF, while heating under vacuum at 150 0 C removes all solvent molecules.
  • the partially and fully evacuated MOFs are designated, respectively, 3' and 4.
  • Void volumes from PLATON 17 for 3' and 4 are 53 and 65%, respectively.
  • Figure 10 summarizes hydrogen uptake data for the "empty cavity” MOF and the six cavity- tailored variants.
  • the range of gravimetric loadings for these otherwise identical compounds spans a rather remarkable factor of four.
  • 19 the variations correlate well with both surface area and pore volume. While illustrating a relatively simple case (cryogenic H 2 uptake), the correlations clearly point to the potential for node-based, post-assembly modification for systematically altering sorption properties.
  • cavity modification of 4 substantially altered the selectivity of the MOF for CO 2 versus methane.
  • the adsorption in MOFs 3', 4, and 4+9 were compared.
  • Single-component adsorption isotherms for CO 2 , N 2 , and CH 4 were measured experimentally in all three MOFs.
  • the selectivities for CO 2 /N 2 and CO 2 /CH 4 mixtures were calculated using ideal adsorbed solution theory (IAST) 20 .
  • Figure 27 shows the adsorption isotherms of CO 2 , N 2 , and CH 4 at 298 K up to 18 bar, measured volumetrically on evacuated samples of 3, 4, and 5.
  • CO 2 is the most strongly adsorbed molecule due to its large quadrupolar moment.
  • CH 4 shows stronger adsorption than N 2 as already reported in all known sorbents. This is attributed to the higher polarizability of CH 4 (26 x 10 " cm “ ) vs. N 2 (17.6 x 10 "25 cm “3 ).
  • Measurement of N 2 isotherms for any of the three MOFs at 77 K could not be made, but the materials did take up N 2 at 298 K.
  • Figure 29 shows the CO 2 /N 2 selectivities in 4+9 at different pressures and different mixture compositions predicted by IAST.
  • the selectivity increased with decreasing pressure.
  • the selectivity increased as y N2 approached unity, but at zero coverage it did not depend on the gas composition.
  • V N2 0.85, which is a typical composition for flue gas from power plants, the selectivity was in the range of 25-45.
  • the selectivity was high (30-37), at or slightly above atmospheric pressure, the pressure regime of interest for removing CO 2 from flue gas.
  • the selectivity of 4+9 was higher than that of Cu-BTC (20-22 as predicted by molecular simulation), the largest previously reported for MOFs. 21
  • these selectivities were considerably higher than the experimental CO 2 /N 2 selectivities reported for zeolite and carbon adsorbents under similar conditions: zeolite 4A (19), zeolite 13X (18), activated carbon (15).
  • TGA Thermogravimetric analyses
  • PXRD Powder X-ray diffraction
  • Adsorption isotherms were measured with an Autosorb 1-MP from Quantachrome Instruments.
  • 1 H NMR and 13 C NMR were done on a Varian Inova 500 spectrometer at 500 MHz and 125 MHz respectively.
  • Adsorption measurements Samples of known weight evacuated at the appropriate temperature under 10 "5 torr dynamic vacuum for 24 hours on an Autosorb 1-MP from Quantachrome Instruments prior to gas adsorption measurements. The evacuated sample was weighed again to obtain the sample weight. Table 2. H 2 uptake, surface areas, and pore volumes
  • ⁇ np ⁇ nN + — ⁇ N' + ⁇ b t N'
  • MOF metal-organic framework
  • MOFs of the invention are a promising material for CO 2 /N 2 separations.
  • they provide preliminary insight into the factors of most importance for adsorption selectivity of CO 2 , N 2 , and CH 4 mixtures in MOFs.
  • Post- synthesis modification of MOFs by replacing coordinated solvent molecules with highly polar ligands or ligands featuring other chemical functionalities may be a powerful method for generating new sorbents for other difficult separations.
  • the present invention can be utilized in the context of gas storage, gas/small molecule separations, gas/small molecules sensing, chemical catalysis and chemical protection.
  • gas/small molecule separations gas/small molecules separations
  • gas/small molecules sensing gas/small molecules sensing
  • chemical catalysis chemical catalysis
  • chemical protection Various aspects and features of this invention can be considered in the context of the following references, as enumerated above.

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Abstract

La présente invention concerne un phényle d'acide carboxylique tétratopique destiné à des composés organométalliques structurants. Ces composés conviennent à la catalyse, au stockage de gaz, à la détection, à l'imagerie biologique, à l'apport médicamenteux et à la séparation par adsorption des gaz.
PCT/US2009/060524 2008-10-10 2009-10-13 Composés tétratopiques du phényle, matière structurante organométallique correspondante, et élaboration après assemblage WO2010042948A2 (fr)

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JP2014189537A (ja) * 2013-03-28 2014-10-06 Jx Nippon Oil & Energy Corp 多孔性金属錯体
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CN111182964A (zh) * 2017-09-19 2020-05-19 阿卜杜拉国王科技大学 用于水吸附相关应用和气体储存的铬基金属-有机骨架
EP3887022A4 (fr) * 2018-11-26 2022-08-17 The Regents of The University of California Structures organométalliques à variables multiples et autres structures organométalliques, et leurs utilisations
JP7008653B2 (ja) * 2019-02-07 2022-01-25 株式会社東芝 分子検出装置
CN111410596B (zh) * 2020-04-02 2021-03-30 浙江大学 一种碳八芳烃同分异构体混合物的分离方法
JP7106612B2 (ja) * 2020-10-01 2022-07-26 株式会社東芝 蛍光発光可能な膜、および分子検出装置
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US9206945B2 (en) 2012-02-15 2015-12-08 Ford Global Technologies, Llc System and method for hydrogen storage
JP2014166971A (ja) * 2013-02-28 2014-09-11 Nippon Steel & Sumitomo Metal 多孔性高分子金属錯体、ガス吸着材、これを用いたガス分離装置およびガス貯蔵装置
JP2014189537A (ja) * 2013-03-28 2014-10-06 Jx Nippon Oil & Energy Corp 多孔性金属錯体
US10519367B2 (en) 2018-03-20 2019-12-31 Kabushiki Kaisha Toshiba Metal organic framework, phosphor film, and molecule detecting device

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US8262775B2 (en) 2012-09-11

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